1:2 cromium complex dyes

ABSTRACT

The present invention relates to novel 1:2 chromium complex dyes, processes for their preparation and their use for dyeing or printing fiber materials containing hydroxyl groups or containing nitrogen.  
     The present invention relates to a 1:2 chromium complex dye of formula (I)  
                 
 
     wherein all substituents are as defined in the claims, a process for their preparation and their use for dyeing or printing fiber materials containing hydroxyl groups or containing nitrogen.

[0001] The present invention relates to novel 1:2 chromium complex dyes,processes for their preparation and their use for dyeing or printingfiber materials containing hydroxyl groups or containing nitrogen.

[0002] The invention relates to a 1:2 chromium complex dye of formula(I)

[0003] wherein

[0004] R₁ is O(CH₂)_(n)OR₂ or (CH₂)nOR₂,

[0005] R₂ is H; linear C₁₋₄alkyl; branched C₃₋₄alkyl or —SO₃H,

[0006] n is 1, 2, 3 or 4 and

[0007] K is a cation

[0008] as well as mixtures thereof and/or salts thereof.

[0009] The linear or branched alkyl groups my be substituted orunsubstituted. Suitable substituents may be for example hydroxyl,halogens, such as Cl or Br or a sulpho-group

[0010] In preferred compounds according to formula (I) R₂ is H;C₁₋₃alkyl or —SO₃H, and n is 1, 2, 3 or 4.

[0011] In more preferred compounds according to formula (I) R₂ is H; CH₃or CH₂CH₃ and n is 2, 3or 4.

[0012] Suitable cations K are alkali metal, alkaline earth metal,ammonium, alkanolammonium or alkylammonium cations. K can also be morethan one cation, for example as in the case of monovalent cations.Examples of corresponding cations are the sodium, lithium or ammoniumcations or mono-, di- or triethanolammonium cations.

[0013] A further embodiment of the present invention is a process forthe production of compounds according to formula (I), which comprisesreacting an azo compound of the formula (II)

[0014] in which R₁, is defined as above

[0015] with a 1:1 chromium complex compound of the formula (III)

[0016] The reaction of the azo compound of the formula (III) with the1:1 chromium complex compound of the formula (II) is carried out, forexample, in an aqueous medium at a temperature of, for example, 40° C.to 130° C., in particular 70° C. to 100° C., at a pH of, for example, 8to 14, in particular at a pH of 10 to 13. The reaction is advantageouslycarried out in the presence of an agent which neutralizes mineral acidor an alkaline agent, for example in the presence of an alkali metalcarbonate, alkali metal acetate or alkali metal hydroxide, sodium beingpreferred as the alkali metal.

[0017] The compounds of the formulae (II) and (III) are known or can beobtained analogously to known processes.

[0018] Compounds of the formula (II) can be obtained by customarydiazotization and coupling reactions. The diazotization is as a rulecarried out by the action of nitrous acid in aqueous-mineral acidsolution at a low temperature, for example 0° C. to 20° C., and thecoupling is advantageously carried out at an alkaline pH, for example ata pH of 8 to 12.

[0019] 1:1 chromium complex compounds of the formula (III) can thus beobtained in accordance with customary chroming processes, in which thereaction can be carried out with the chromium salt, for example in anaqueous medium, if appropriate under pressure, at a temperature of, forexample, 90° C. to 130° C. Chromium salts are, for example,chromium(III) acetate, chromium(III) nitrate, chromium(III) chloride,chromium(III) salicylate or, in particular, chromium(III) sulfate.

[0020] A further embodiment of the invention is a process for dyeing orprinting fiber materials containing hydroxyl groups or containingnitrogen.

[0021] Fiber materials are preferably either naturally occurringpolyamide fiber materials, for example silk or, in particular, wool, orsynthetic polyamide fiber materials, for example polyamide 6 orpolyamide 6,6, or wool- or polyamide-containing blend fabric. Syntheticpolyamide fiber materials are of particular interest here.

[0022] The above fiber material can be in the most diverse processingforms, for example as fiber, yarn, woven fabric or knitted fabric, andin particular in the form of carpets.

[0023] The dyeing or printing can be carried out in customary dyeing orprinting apparatuses. The dye liquors or printing pastes can comprisefurther additives, for example wetting agents, antifoams, levelingagents or agents which influence the properties of the textile material,for example softening agents, additives for providing a flame-resistantfinish or soil-, water- and oil-repellent agents, as well aswater-softening agents and naturally occurring or synthetic thickeners,for example alginates and cellulose ethers.

[0024] In a preferred printing process, the padding method is used, forexample pad-steam, pad-thermofix, pad-dry, pad-batch, pad-jig andpad-roll. Alternatively, printing may be carried out using ink-jetmethods.

[0025] The 1:2 chromium complex dyes of the formula (I) according to theinvention give level dyeings with good all-round properties. The 1:2chromium complex dyes of the formula (I) according to the invention isalso suitable as a component in a dyeing mixture.

[0026] The examples below serve to illustrate the invention. Unlessstated otherwise, the percentages are by weight, and the degrees aregiven in Celsius.

EXAMPLE 1A

[0027] A solution of 71.7 parts of 1-acetylamino-2-hydroxybenzene in 200parts of water at 0-5° C. are mixed with a diazonium salt solutionformed at 0-5° C. and a pH of 1 from a mixture of 76.6 parts of4-amino-1 -(2′-hydroxyethoxy)-benzene and 125 parts by volume of 4Nsodium nitrite solution. During the coupling reaction the pH ismaintained at 12-13by the continuous adding of a 30% sodium hydroxidesolution. At the end of the reaction the product obtained is salted out,filtered by suction and dried. The still damp residue after suctionfiltration is dissolved in 550 parts of 4% by weight solution of sodiumhydroxide and the resultant solution is heated to 90-100° C. until thesaponification of the acetyl group is complete as determined by thinlayer chromatography. Then the solution is neutralized with hydrochloricacid, salted-out, filtered by suction and dried. The compound thusobtained having the formula (IIa)

EXAMPLE 1B 136.6 parts of the monoazo-compound obtained according toExample 1a is dissolved in 300 parts of water and diazotized by themethod described in Example 1a. 72.0 parts of 2-hydroxy-naphthalene isdissolved in a mixture of 300 parts of water and 100 parts of a 30%sodium hydroxide solution. Then the diazo-compound is added during 1 hand at 20-25° C. to this solution. At the same time a 30% sodiumhydroxide solution is added continuously in order to maintain the pH ofthe mixture at 12-13. After coupling reaction is completed the bisazocompound thus formed is salted-out using conventional methods, filteredand dried at 60° C. under vacuum. The product has the formula (IIb)

[0028]

EXAMPLE 1C

[0029] 214.2 parts of the bisazo-compound obtained according to Example1b is suspended in 1300 parts of water at 75-80° C. and a pH of 11-12.To this mixture 248.5 parts of the 1:1 chromium complex having theformula (IIIa)

[0030] obtained by conventional methods, is added while stirring. At thesame time the pH is kept at 11 by the addition of a 30% sodium hydroxidesolution. After reaction is completed the resulting 1:2 chromium complexis salted-out using conventional methods, filtered and dried at 60° C.under vacuum. The end product conforms to the formula (IV)

[0031] and dyes wool and synthetic polyamides to a black shade. Dyeingsthus obtained display excellent light and wet fastness properties.

EXAMPLES 2-11

[0032] Table 1 discloses several dyestuffs which are formed according tothe method analogous to this described in Examples 1a to 1c employingcorresponding starting materials. In all cases the dyestuff obtaineddyes wool and synthetic polyamides to a black shade and dyeings thusobtained display excellent light and wet fastness properties. TABLE 1

Example R 2 —CH₂CH₂OH 3 —CH₂OH 4 —CH₂CH₂CH₂OH 5 —CH₂CH₂CH₂CH₂OH 6—OCH₂CH₂OCH₃ 7 —OCH₂CH₂OCH₂CH₃ 8 —CH₂CH₂OCH₃ 9 —CH₂CH₂OCH₂CH₃ 10—OCH₂CH₂OSO₃H

APPLICATION EXAMPLE A

[0033] A dyebath at 40° C., consisting of 2000 parts of water, 1 part ofa weakly cation-active leveling agent which is based on an ethoxylatedaminopropyl fatty acid amide and which has affinity for dye, 1.5 partsof the dye of Example 1 and adjusted to pH 6 with 0.5 parts of 40%acetic acid is entered with 100 parts of nylon-6 fabric. After 10minutes at 40° C., the dyebath is heated to 98° C. at a rate of 1° C.per minute and then left at the boil for 45-60 minutes. Thereafter it iscooled down to 70° C. over 15 minutes. The dyeing is removed from thebath, rinsed with hot and then with cold water and dried. The resultobtained is a grey polyamide dyeing possessing very high lighffastness.

[0034] Similarly, the dyestuffs of Examples 2 to 10 or mixtures of theexemplified dyestuffs are employed to print cotton in accordance withthe method given in Application Example A. All prints obtained are navyand show good fastness properties.

APPLICATION EXAMPLE B

[0035] A dyebath at 40° C., consisting of 4000 parts of water, 1 part ofa weakly amphoteric leveling agent which is based on a sulfated,ethoxylated aminopropyl fatty acid amide and which has affinity for dye,2 parts of the dye of Example 1 and adjusted to pH 6 with 0.5 parts of40% acetic acid is entered with 100 parts of wool fabric. After 10minutes at 40° C., the dyebath is heated to boiling at a rate of 1° C.per minute and then left at the boil for 45-60 minutes. Thereafter it iscooled down to 70° C. over 20 minutes. The dyeing is removed from thebath, rinsed with hot and then with cold water and dried. The resultobtained is a grey wool dyeing possessing very high lighffastness.

[0036] Similarly, the dyestuffs of Examples 2 to 10 or mixtures of theexemplified dyestuffs are employed to print cotton in accordance withthe method given in Application Example B. All prints obtained are navyand show good fastness properties.

APPLICATION EXAMPLE C

[0037] 100 parts of a woven nylon-6 material are padded with a 50° C.liquor consisting of  40 parts of the dye of Example 1, 100 parts ofurea,  20 parts of a nonionic solubilizer based on butyldiglycol, 15-20parts of acetic acid (to adjust pH to 4),  10 parts of a weaklycation-active leveling agent which is based on an ethoxylatedaminopropyl fatty acid amide and has affinity for dye and 810-815 partsof water (to make up to 1000 parts of padding liquor).

[0038] The material thus impregnated is rolled up and left to dwell in asteaming chamber under saturated steam conditions at 85-98° C. for 3-6hours for fixation. Then the dyeing is rinsed with hot and cold waterand dried. The result obtained is a grey nylon dyeing having goodlevelness in the piece and good lighffastness.

[0039] Similarly, the dyestuffs of Examples 2 to 10 or mixtures of theexemplified dyestuffs are employed to print cotton in accordance withthe method given in Application Example C. All prints obtained are navyand show good fastness properties.

APPLICATION EXAMPLE D

[0040] A textile cut pile sheet composed of nylon-6 and having asynthetic base fabric is padded with a liquor containing per 1000 parts

[0041] 2 parts of dye of Example 1

[0042] 4 parts of a commercially available thickener based on carobflour ether

[0043] 2 parts of a nonionic ethylene oxide adduct of a higheralkylphenol

[0044] 1 part of 60% acetic acid.

[0045] This is followed by printing with a paste which contains per 1000parts the following components:

[0046] 20 parts of commercially available alkoxylated fatty alkylamine(displace product)

[0047] 20 parts of a commercially available thickener based on carobflour ether.

[0048] The print is fixed for 6 minutes in saturated steam at 100° C.,rinsed and dried. The result obtained is a level-colored cover materialhaving a grey and white pattern.

[0049] Similarly, the dyestuffs of Examples 2 to 10 or mixtures of theexemplified dyestuffs are employed to print cotton in accordance withthe method given in Application Example D. All prints obtained are navyand show good fastness properties.

APPLICATION EXAMPLE E

[0050] 2.5 parts of the dyestuff obtained in Example 1 are dissolvedwith stirring at 25° C. in a mixture of 20 parts diethyleneglycol and77.5 parts water to obtain a printing ink suitable for ink jet printing.

[0051] The dyestuffs of Examples 2 to 10 or dyestuff mixtures ofExamples 1 to 10 can also be used in a manner analogous to thatdescribed in Application Example E.

1. A 1:2 chromium complex dye of formula (I)

wherein R₁ is O(CH₂)_(n)OR₂ or (CH₂)nOR₂, R₂ is H; linear C₁₋₄alkyl;branched C₃₋₄alkyl or —SO₃H, nis 1, 2, 3 or 4 and K is a cation.
 2. A1:2 chromium complex dye of formula (I) according to claim 1, wherein R₂is H; CH₃ or CH₂CH₃ and n is 2, 3 or
 4. 3. A process for the productionof compounds of formula (I) according to claim 1 comprising the step ofreacting an azo compound of the formula (II)

in which R₁ is defined as in claim 1 with a 1:1 chromium complexcompound of the formula (III)


4. An ink-jet ink comprising at least one 1:2 chromium complex dyeaccording to claim 1 or its salt.
 5. A process for dyeing a fibermaterial containing hydroxyl groups or containing nitrogen comprisingthe step of dyeing the fiber material with at least one compoundaccording to formula (I), of claim 1, or its salt.
 6. A fiber materialcontaining hydroxyl groups or containing nitrogen comprising at leastone compound as defined in claim 1, or its salt.
 7. A salt of a 1:2chromium complex dye as claimed in claim
 1. 8. A process for printing afiber material containing hydroxyl groups or containing nitrogencomprising the step of printing the fiber material with at least onecompound according to formula (I) of claim 1, or its salt.